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WO1991008168A1 - Procede de preparation de phases reactives de dioxyde de silicium - Google Patents

Procede de preparation de phases reactives de dioxyde de silicium Download PDF

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Publication number
WO1991008168A1
WO1991008168A1 PCT/EP1990/001946 EP9001946W WO9108168A1 WO 1991008168 A1 WO1991008168 A1 WO 1991008168A1 EP 9001946 W EP9001946 W EP 9001946W WO 9108168 A1 WO9108168 A1 WO 9108168A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
silicon dioxide
quartz
reaction
cristobalite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1990/001946
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German (de)
English (en)
Inventor
Johannes W. Hachgenei
Rudolf Novotny
Hans Dolhaine
Peter Christophliemk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1991008168A1 publication Critical patent/WO1991008168A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid

Definitions

  • the invention relates to a method for producing reactive silicon dioxide phases from quartz sand.
  • the reactive phases consist of cristobalite, tridymite, amorphous silicon dioxide and alkali metal silicate and are characterized by a small proportion of quartz.
  • Tridymite and cristobalite have a more open structure than quartz, which is also reflected in the different densities (2.65 g / cm3 for quartz, approx.2.3 g / c ⁇ .3 for tridymite and cristobalite) and in the increased reactivity, e.g. for the hydrothermal production of sodium polysilicates.
  • Cristobalite which because of its white color and for controlling the coefficient of expansion is used primarily as a raw material and filler, for example in ceramic products, but also for the production of colors.
  • Cristobalite is produced by converting quartz sands in a rotary kiln at temperatures of approx. 1500 ° C with the addition of alkali (Ullmann's Encyklopadie der Technischen Chemie, 4th edition, Verlag Chemie, Weinheim, Volume 21 (1982), page 442).
  • EP-A-0283933 describes the production of cristobalite from amorphous silicon dioxide with a specific surface area at a temperature between 1000 and 1300 ° C.
  • the amorphous silicon dioxide has to be produced for this purpose and is already characterized by an increased reactivity.
  • Alkali metal compounds containing lithium, sodium or potassium are proposed as catalysts for this reaction. These compounds are used in very small amounts since they then have to be removed from the cristobalite again by treatment at temperatures above 1300 ° C. The entire process is characterized by very long reaction times.
  • tridymite is stable at all without impurities. Larger quantities of accompanying elements (alkali metals, aluminum) favor the formation of tridymite, which often has many structural defects in the crystal structure. According to Novakovic et al (Interceram, (1986) pages 29-30), the conversion to tridymite (1350 ° C, 114 hours, Li catalysis) first takes place via cristobalite, which converts to tridymite in a second step.
  • the object of the present invention was to provide reactive silicon dioxide phases from quartz sand which are distinguished by a very low quartz content.
  • the reaction temperatures and especially the reaction times should be shorter or shorter than those of known processes.
  • the object was achieved according to the invention by a process for the production of reactive silicon dioxide phases, which is characterized in that quartz sand is mixed with an alkali metal compound or its aqueous solution, the alkali metal compound being selected from the group of compounds which are used in the Heating into the corresponding alkali metal oxides, that the molar ratio of SiO 2 to alkali metal oxide is between 1: 0.0025 and 1: 0.1 and that this mixture is heated to a temperature between 1100 ° C. and 1700 ° C.
  • a molar ratio of SiO 2 to alkali metal oxide is mentioned here and also below, this means the molar ratio of the silicon dioxide contained in the quartz sand to the alkali metal oxide, based on the alkali metal compound used in each case.
  • the reactive silicon dioxide phases obtained according to this process consist of cristobalite, tridymite, amorphous silicon dioxide and alkali metal silicate and are characterized by a small proportion of quartz, as determined by X-ray diffraction analyzes.
  • reaction times decrease with increasing reaction temperature and decrease especially from 1300 ° C.
  • a catalyst addition of 5% by weight sodium hydroxide corresponding to a molar ratio of silicon dioxide to alkali metal oxide of 1: 0.0375, after a reaction time of 30 minutes no residual quartz was detectable in the reaction product of this example .
  • reaction temperatures can be increased still further, as a result of which the reaction time, based on a specific catalyst, can be shortened further. Lowering the temperature to 1200 ° C leads to an increase in the residual quartz content.
  • Molar ratios of silicon dioxide to alkali metal oxide of 1: 0.0035 to 1: 0.05 have proven to be particularly preferred for carrying out the reaction, for example an addition of 0.45% by weight to 6.45% by weight in the case of sodium hydroxide speaks. Applied to the addition of potassium hydroxide, this corresponds to 0.63% by weight to 9.0% by weight.
  • alkali metal compounds which convert to the corresponding alkali metal oxides on heating can be used as catalysts.
  • These are in particular lithium, sodium or potassium hydroxide, as well as the carbonates, nitrates, nitrites, sulfates, sulfites, oxalates or formates of these alkali metals.
  • a particularly uniform distribution of the catalyst over the quartz sand is achieved by applying a 5 to 50% strength by weight aqueous solution or slurry of the alkali metal compound to the quartz sand.
  • Particularly suitable concentrations of these solutions are between 15 and 25% by weight.
  • the quartz sand is mixed with the appropriate amount of an alkali metal compound or its aqueous solution and annealed in a muffle furnace, rotary kiln or shaft furnace for a defined time.
  • the use of rotary kilns is particularly recommended for carrying out the process on a larger scale.
  • Example 1 the samples were annealed at a temperature of 1400 ° C. With the addition of 0.5% by weight of sodium hydroxide in the form of an aqueous solution, 90% of the quartz has already reacted after 15 minutes. With a catalyst amount of 5% by weight sodium hydroxide, no quartz is left in the samples after 30 minutes Find. With 0.5% by weight sodium hydroxide addition, the reaction is complete within one hour.
  • reaction proceeds more slowly at a temperature of 1300 ° C. (example 2a-c), but even then, with a catalyst amount of 5% by weight, 97% of the quartz has reacted within half an hour.
  • reaction temperature of 1200 ° C. does not lead to a complete conversion of the quartz into reactive phases within 3 hours, but conversions of more than 80% are also achieved here.
  • a reaction temperature of at least 1300 ° C, i.e. in the range from 1300 to 1700 ° C. is therefore particularly preferred.
  • the process is carried out at reaction times of 10 to 180 minutes, in particular less than 60 minutes - i.e. at reaction times in the range from 10 to 60 minutes.
  • Example 6 shows the results of the reaction catalyzed by the addition of sodium sulfate - in aqueous solution.
  • Example 7 shows the results of the reaction catalyzed by lithium hydroxide, likewise in aqueous solution.
  • amorphous phases consist of alkali metal silicates and amorphous silicon dioxide.
  • the proportions of alkali metal silicate are due to the alkali metal compounds involved in the reaction.
  • the quartz sand reacted contained> 99.9% silicon dioxide and was of natural origin.
  • the respective alkali metal compound was dissolved in just enough water that the quartz sand was covered with the solution. Then it was slowly dried and the dry sand was mixed vigorously.
  • the two solid components were intimately mixed with one another before the reaction and heated over a period of between 10 and 180 minutes, preferably less than 60 minutes.
  • a glazed alumina crucible served as the reaction vessel.
  • Table 1 Temperatures and reaction times for the individual examples are shown in Table 1 below. In addition to the proportion by weight of alkali metal compound, Table 1 also gives the molar ratio of S1O2 to alkali metal oxide.
  • Ratio of cristobalite tridymite in tempered quartz sands (estimate from RBA diagrams)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation de phases réactives de dioxyde de silicium, caractérisé en ce qu'on mélange du sable quartzeux avec un composé d'un métal alcalin ou sa solution aqueuse, ledit composé de métal alcalin étant choisi dans le groupe de composés se transformant, par chauffage, en l'oxyde de métal alcalin correspondant, suivant un rapport molaire de SiO2 à l'oxyde de métal alcalin compris entre 1:0,0025 et 1:0,1, et en ce qu'on chauffe ce mélange à une température comprise entre 1100 °C et 1700 °C.
PCT/EP1990/001946 1989-11-23 1990-11-14 Procede de preparation de phases reactives de dioxyde de silicium Ceased WO1991008168A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3938730.5 1989-11-23
DE19893938730 DE3938730A1 (de) 1989-11-23 1989-11-23 Verfahren zur herstellung von reaktiven siliziumdioxid-phasen

Publications (1)

Publication Number Publication Date
WO1991008168A1 true WO1991008168A1 (fr) 1991-06-13

Family

ID=6393998

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/001946 Ceased WO1991008168A1 (fr) 1989-11-23 1990-11-14 Procede de preparation de phases reactives de dioxyde de silicium

Country Status (7)

Country Link
CN (1) CN1055908A (fr)
AU (1) AU6713890A (fr)
DE (1) DE3938730A1 (fr)
IE (1) IE904222A1 (fr)
PL (1) PL287885A1 (fr)
WO (1) WO1991008168A1 (fr)
YU (1) YU220390A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012433A1 (fr) * 1992-11-27 1994-06-09 Crosfield Limited Cristobalite
EP0889004A1 (fr) * 1997-07-01 1999-01-07 Clariant GmbH Procédé de préparation d'un silicate en couches synthétique de type hectorite
US7537653B2 (en) * 2005-01-31 2009-05-26 Gcc Technology And Processes S.A. Microsilica materials with improved pozzolanic activity

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555798B1 (fr) * 1992-02-13 1999-05-06 Becton, Dickinson and Company Célite hydrate et purification d'ADN
RU2145948C1 (ru) * 1999-06-03 2000-02-27 Общество с ограниченной ответственностью "Кирилишин и партнеры" Способ изготовления декоративно-облицовочных изделий
FR2933392B1 (fr) * 2008-07-04 2011-04-22 Rhodia Operations Procede de preparation de silice precipitee a partir de metabisulfite ou sulfite de sodium
CN105419242A (zh) * 2015-12-31 2016-03-23 珠海云智新材料科技有限公司 一种掺杂空心漂珠的吸音环氧树脂材料及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Interceram, no. 5, 1986, (Freiburg, DE), R. Novakovic et al.: "Kinetics and mechanism of Quartz-tridymite transformation", siehe Seiten 29-30 *
Ullmanns Encyklop{die der technischen Chemie, 4., neubearbeitete und erweiterte Auflage, Band 21, "Schwefel bis Sprengstoffe", 1982, Verlag Chemie, (Weinheim, DE), siehe Seite 442 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012433A1 (fr) * 1992-11-27 1994-06-09 Crosfield Limited Cristobalite
EP0889004A1 (fr) * 1997-07-01 1999-01-07 Clariant GmbH Procédé de préparation d'un silicate en couches synthétique de type hectorite
US7537653B2 (en) * 2005-01-31 2009-05-26 Gcc Technology And Processes S.A. Microsilica materials with improved pozzolanic activity

Also Published As

Publication number Publication date
DE3938730A1 (de) 1991-05-29
CN1055908A (zh) 1991-11-06
AU6713890A (en) 1991-06-26
YU220390A (sh) 1993-10-20
IE904222A1 (en) 1991-06-05
PL287885A1 (en) 1991-12-02

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